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Critical Evaluation of Proven Chemical Weapon Destruction Technologies

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Pure Appl. Chem., Vol. 74, No. 2, pp. 187–316, 2002. © 2002 IUPAC INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY ORGANIC AND BIOMOLECULAR CHEMISTRY DIVISION IUPAC COMMITTEE ON CHEMICAL WEAPON DESTRUCTION TECHNOLOGIES* WORKING PARTY ON EVALUATION OF CHEMICAL WEAPON DESTRUCTION TECHNOLOGIES** CRITICAL EVALUATION OF PROVEN CHEMICAL WEAPON DESTRUCTION TECHNOLOGIES (IUPAC Technical Report) Prepared for publication by GRAHAM S. PEARSON1,‡ AND RICHARD S. MAGEE2 1Department of Peace Studies, University of Bradford, Bradford, West Yorkshire BD7 1DP, UK 2Carmagen Engineering, Inc., 4 West Main Street, Rockaway, NJ 07866, USA *Membership of the IUPAC Committee is: Chairman: Joseph F. Burnett; Members: Wataru Ando (Japan), Irina P. Beletskaya (Russia), Hongmei Deng (China), H. Dupont Durst (USA), Daniel Froment (France), Ralph Leslie (Australia), Ronald G. Manley (UK), Blaine C. McKusick (USA), Marian M. Mikolajczyk (Poland), Giorgio Modena (Italy), Walter Mulbry (USA), Graham S. Pearson (UK), Kurt Schaffner (Germany). **Membership of the Working Group was as follows: Chairman: Graham S. Pearson (UK); Members: Richard S. Magee (USA), Herbert de Bisschop (Belgium). The Working Group wishes to acknowledge the contributions made by the following, although the conclusions and contents of the Technical Report remain the responsibility of the Working Group: Joseph F. Bunnett (USA), Charles Baronian (USA), Ron G. Manley (OPCW), Georgio Modena (Italy), G. P. Moss (UK), George W. Parshall (USA), Julian Perry Robinson (UK), and Volker Starrock (Germany). ‡Corresponding author Republication or reproduction of this report or its storage and/or dissemination by electronic means is permitted without the need for formal IUPAC permission on condition that an acknowledgment, with full reference to the source, along with use of the copyright symbol ©, the name IUPAC, and the year of publication, are prominently visible. Publication of a translation into another language is subject to the additional condition of prior approval from the relevant IUPAC National Adhering Organization. 187 188 G. S. PEARSON AND R. S. MAGEE Critical evaluation of proven chemical weapon destruction technologies (IUPAC Technical Report) Abstract: A critical evaluation is made of the chemical weapon destruction tech- nologies demonstrated for 1 kg or more of agent in order to provide information about the technologies proven to destroy chemical weapons to policy-makers and others concerned with reaching decisions about the destruction of chemical weapons and agents. As all chemical agents are simply highly toxic chemicals, it is logical to consider the destruction of chemical agents as being no different from the consideration of the destruction of other chemicals that can be as highly toxic—their destruction, as that of any chemicals, requires the taking of appropri- ate precautions to safeguard worker safety, public health, and the environment. The Chemical Weapons Convention that entered into force in 1997 obliges all States Parties to destroy any stockpiles of chemical weapons within 10 years from the entry into force of the Convention—by 2007—with the possibility of an exten- sion for up to 5 years to 2012. There is consequently a tight timeline under the treaty for the destruction of stockpiled chemical weapons and agents—primarily held in Russia and the United States. Abandoned or old chemical weapons— notably in Europe primarily from World War I, in China from World War II as well as in the United States—also have to be destroyed. During the past 40 years, more than 20 000 tonnes of agent have been destroyed in a number of countries and over 80 % of this has been destroyed by incineration. Although incineration is well proven and will be used in the United States to destroy over 80 % of the U.S. stockpile of 25 800 tonnes of agent, considerable attention has been paid particu- larly in the United States to alternative technologies to incineration because of several constraints that are specific to the United States. Much of the information in this report is based on U.S. experience—as the United States had, along with the Russian Federation, by far the largest stockpiles of chemical weapons and agents anywhere in the world. The United States has made much progress in destroying its stockpile of chemical weapons and agents and has also done more work than any other country to examine alternative technologies for the destruction of chem- ical weapons and agents. However, the national decisions to be taken by countries faced with the destruction of chemical weapons and agents need to be made in the light of their particular national conditions and standards—and thus may well result in a decision to use different approaches from those adopted by the United States. This report provides information to enable countries to make their own informed and appropriate decisions. © 2002 IUPAC, Pure and Applied Chemistry 74, 187–316 Critical evaluation of proven chemical weapon destruction technologies 189 CONTENTS INTRODUCTION 190 I. MANDATE FOR DESTRUCTION 194 II. OVERALL PERSPECTIVE 202 A. Experience in the destruction of chemical weapons 202 B. Chemical weapons awaiting destruction 207 C. Summary 212 III. NATURE OF THE PROBLEM 213 IV. TRANSPORT OF CHEMICAL WEAPONS AND BULK AGENT 216 A. Introduction 216 B. Experience 216 C. Risk perspectives 220 V. REMOVAL OF CHEMICAL AGENTS FROM CHEMICAL WEAPONS 223 A Disassembly and draining 223 B. Explosive charges for accessing chemical weapons 224 C. Water-jet technology for munitions cleaning and cutting 225 D. Cryofracture 226 VI. HIGH-TEMPERATURE DESTRUCTION OF CHEMICAL AGENTS 230 A. Incineration 230 B. Plasma pyrolysis 239 C. Molten metal technology 244 D. Hydrogenolysis 247 E. Destruction of arsenicals 251 VII. LOW-TEMPERATURE DESTRUCTION OF CHEMICAL AGENTS 258 A. Hydrolysis of mustard agent HD 258 B. Hydrolysis of mustard and nerve agents using aqueous sodium hydroxide 262 C. Reaction of mustard and nerve agents using amines and other reagents 265 D. Electrochemical oxidation 267 E. Solvated electron technology (SET) 272 VIII. EFFLUENT TREATMENT 276 A. Gas 276 B. Liquid 280 C. Solid 289 IX. DEALING WITH OLD RECOVERED MUNITIONS 291 A. Transportation of old chemical weapons 294 B. Identification 295 C. Removal of chemical warfare agents from munitions 295 D. Destruction including mobile destruction facilities 297 E. Transport of toxic waste 297 F. Chemical weapons abandoned by Japan in China 298 G. U.S. Army Non-Stockpile Chemical Materiel Project 300 X. TECHNOLOGY COMPARISONS 305 XI. TECHNOLOGIES AND CONSTRAINTS: MAKING INFORMED DECISIONS 309 GLOSSARY OF ACRONYMS 314 © 2002 IUPAC, Pure and Applied Chemistry 74, 187–316 190 G. S. PEARSON AND R. S. MAGEE INTRODUCTION 1. The aim of the IUPAC Working Party on Evaluation of Chemical Weapon Destruction Technologies has been to provide information about the technologies that have been proven to destroy chemical weapons to policy-makers and others concerned with reaching decisions about the destruction of chemical weapons and agents. The Working Party has recognized that each country faced with destruction of chemical weapons will need to take decisions on how to achieve this by considering both the quantity and nature of the chemical weapons in that country, the requirements of the Chemical Weapons Convention, and its own national laws and regulations in deciding where and how to destroy them safely with minimum impact on public health and the environment. Consequently, this report is designed to provide appropriate and relevant informa- tion on the proven available destruction technologies in order to help countries arrive at informed national decisions appropriate for that country. 2. The Working Party has examined the technologies for the destruction of chemical weapons that have been demonstrated on 1 kg or more of toxic chemical agent. In carrying out this study, the Working Party has first taken note of the mandate for destruction that stems from the requirements of the Chemical Weapons Convention (CWC) opened for signature in January 1993, entered into force on 29 April 1997 and, in December 2001, has 144 States Parties [1]. The CWC requires that all declared chemical weapons be destroyed within 10 years after the entry into force of the Convention—in other words, by 29 April 2007—with a possible extension, should that be neces- sary, for up to five years to 29 April 2012. The CWC also sets out requirements for the destruc- tion of old and abandoned chemical weapons [2] that will continue to be found for decades in countries where chemical weapons have been produced, tested, stored, and used. There are thus two principal categories of chemical weapons: a. Stockpiled chemical weapons, which have to be destroyed by 29 April 2007 with a possi- ble extension to 29 April 2012; and b. Old and abandoned chemical weapons, in unknown types and quantities, which will be found from time to time and will need to be destroyed also by 29 April 2007 unless the Executive Council decides to modify the provisions on the time limit. 3. A historical perspective is then provided giving an indication of the nature of the chemicals that have been used as chemical weapons during the past century and then addresses the nature of the problem. Many chemical weapons have been destroyed or disposed of by methods that are no longer accepted—and indeed, the CWC specifically prohibits dumping in any body of water, land burial, and open pit burning. During the past 40 years, over 20 000 agent-tonnes of chem- ical weapons have been destroyed; more than 80 % by incineration and the remainder by neu- tralization. It should be noted that the unit used in this report for the quantities of chemical weapons destroyed is agent-tonnes and not the weight of munitions. Following the entry into force of the CWC, a total figure has been published by the Organization for the Prohibition of Chemical Weapons (OPCW) for the chemical agents declared and destroyed. The figure as of 30 June 2001 for the total declared is 69 862 agent-tonnes, and the total destroyed is 5 734 agent- 1.
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